Marcelo Vilches-Herrera

Bio: Marcelo Vilches-Herrera is an academic researcher from University of Rostock. The author has contributed to research in topics: Aminopyridines & Regioselectivity. The author has an hindex of 8, co-authored 11 publications receiving 332 citations.

Isomerization–Hydroformylation Tandem Reactions

Abstract: The metal-catalyzed isomerization–hydroformylation tandem reaction is of great importance for the production of linear aldehydes starting from internal olefins, but also, the shift of the double bond from a terminal position into the interior of an alkyl chain and the subsequent hydroformylation can be of interest. This review aims to summarize problems and achievements in this area under particular consideration of results published by the Leibniz-Institut fur Katalyse (LIKAT) in the past two decades. A main focus is given to the variation of metals (Co, Rh, Ru, Pd, Pt, Fe) and phosphorus ligands used for the tandem reaction.

One-pot, three-component synthesis of 7-azaindole derivatives from N-substituted 2-amino-4-cyanopyrroles, various aldehydes, and active methylene compounds.

Abstract: An efficient and practical route to 7-azaindole framework has been developed by one-pot, three-component cyclocondensation of N-substituted 2-amino-4-cyanopyrroles, various aldehydes, and active methylene compounds in ethanol or acetic acid at reflux. Reactions involving tetronic acid, indane-1,3-dione, dimedone, and 5-phenylcyclohexane-1,3-dione gave carbocyclic fused 7-azaindoles, whereas Meldrum’s acid, benzoylacetonitrile, and malononitrile resulted in the highly substituted 7-azaindole derivatives, making this strategy very useful in diversity-oriented synthesis (DOS).

3-Methoxalylchromone—a novel versatile reagent for the regioselective purine isostere synthesis

Abstract: The first synthesis of 3-methoxalylchromone was described. The reaction of the latter with electron-rich aminoheterocycles afforded a set of heteroannelated pyridines bearing a CO2Me substituent located at the α-position of the pyridine core.

Remote functionalization through alkene isomerization

Abstract: Exploiting the reactivity of one functional group within a molecule to generate a reaction at a different position is an ongoing challenge in organic synthesis. Effective remote functionalization protocols have the potential to provide access to almost any derivatives but are difficult to achieve. The difficulty is more pronounced for acyclic systems where flexible alkyl chains are present between the initiating functional group and the desired reactive centres. In this Review, we discuss the concept of remote functionalization of alkenes using metal complexes, leading to a selective reaction at a position distal to the initial double bond. We aim to show the vast opportunity provided by this growing field through selected and representative examples. Our aim is to demonstrate that using a double bond as a chemical handle, metal-assisted long-distance activation could be used as a powerful synthetic strategy.

Walking Metals for Remote Functionalization.

Abstract: The distant and selective activation of unreactive C–H and C–C bonds remains one of the biggest challenges in organic chemistry. In recent years, the development of remote functionalization has received growing interest as it allows for the activation of rather challenging C–H and C–C bonds distant from the initiation point by means of a “metal-walk”. A “metal-walk” or “chain-walk” is defined by an iterative series of consecutive 1,2- or 1,3-hydride shifts of a metal complex along a single hydrocarbon chain. With this approach, simple building blocks or mixtures thereof can be transformed into complex scaffolds in a convergent and unified strategy. A variety of catalytic systems have been developed and refined over the past decade ranging from late-transition-metal complexes to more sustainable iron- and cobalt-based systems. As the possibilities of this field are slowly unfolding, this area of research will contribute considerably to provide solutions to yet unmet synthetic challenges.

Mild and Regioselective Benzylic C–H Functionalization: Ni-Catalyzed Reductive Arylation of Remote and Proximal Olefins

Abstract: The synergistic combination of NiH-catalyzed alkene isomerization with nickel-catalyzed cross-coupling has yielded a general protocol for the synthesis of a wide range of structurally diverse 1,1-diarylalkanes in excellent yields and high regioselectivities from readily accessible olefin starting materials. Furthermore, the practicality and synthetic flexibility of this approach is highlighted by the successful employment of isomeric mixtures of olefins for regioconvergent arylation.

Positional and Geometrical Isomerisation of Alkenes: The Pinnacle of Atom Economy.

Abstract: Strategies to achieve spatiotemporal regulation of pre-existing alkenes via external stimuli are essential given the ubiquity of feedstock olefins in chemistry and their downstream applications. Mirroring the 1-0 switch that underpins mammalian vision through selective geometric isomerisation in retinal, strategies to manipulate 2D space by both geometric and positional isomerisation of alkenes via chemical, thermal and light-driven processes are being intensively pursued. This minireview highlights the current state of the art in activating and achieving directionality in these fundamental chemical transformations.